Trimethylsilylacetylene → 4-(Trimethylsilylethynyl)benzaldehyde

HRID 2262332Notes

Reaction equation

HRID 2262332 reaction equation
I[C:2]1[CH:9]=[CH:8][C:5]([CH:6]=[O:7])=[CH:4][CH:3]=1.[CH3:10][Si:11]([C:14]#[CH:15])([CH3:13])[CH3:12].C(N(C(C)C)CC)(C)C>O1CCCC1.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu](I)I>[CH3:10][Si:11]([C:14]#[C:15][C:2]1[CH:9]=[CH:8][C:5]([CH:6]=[O:7])=[CH:4][CH:3]=1)([CH3:13])[CH3:12]

Participants

7

Reactant 3

HCID 66111TrimethylsilylacetyleneHCID 81531DiisopropylethylamineHCID 966574-Iodobenzaldehyde

Product 1

HCID 27716434-(Trimethylsilylethynyl)benzaldehydeYield 98%

Reagents, catalysts & solvents 3

HCID 83717Copper iodideCatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8028TetrahydrofuranSolvent

Procedure

As shown in the following Reaction 6, 500 mg (2.15 mmol) of 4-iodobenzaldehyde was melted in 2.7 mL of tetrahydrofuran, and 0.45 mL (3.22 mmol, 1.5 eq) of trimethylsilylacetylene, 0.6 mL (3.44 mmol, 1.6 eq) of diisopropylethylamine (DIEA), 7 mg (0.01 mmol, 0.5 mol %) of dichlorobis-(triphenylphosphine)palladium(II), and 3 mg (0.02 mmol, 1 mol %) of copper iodide was added thereto, and then the reaction solution was stirred under nitrogen atmosphere for 12 hours at room temperature. Next, the reaction solution was filtered with ether, and then was extracted with 1M sodium chloride aqueous solution 1 time. The organic solvent layer was dehydrated with magnesium sulfate, filtered, and then distilled under reduced pressure. The compound distilled under reduced pressure was purified with a column chromatography (mobile phase volume ratio; ethylacetate:n-hexane=1:10) to obtain 420 mg of 4-trimethylsilylethynyl benzaldehyde with the yield of 98%. NMR data of the obtained compound is as follows. [1H NMR (400 MHz, CDCl3): δ 9.81 (s, 1H), 7.63 (d, 2H), 7.42 (d, 2H), 0.13 (s, 9H)].

Workup

  1. filtrationNext, the reaction solution was filtered with ether
  2. extractionwas extracted with 1M sodium chloride aqueous solution 1 time
  3. filtrationfiltered
  4. distillationdistilled under reduced pressure
  5. distillationThe compound distilled under reduced pressure
  6. customwas purified with a column chromatography (mobile phase volume ratio; ethylacetate:n-hexane=1:10)

Sources & evidence

ORD record
ord-559326e40f194987824f979be23c60e1
Source dataset
uspto-grants-2010_12
Patent number
US07850872B2

Reaction notes

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